Perfluoropolyether Polymer

Abstract

The present invention relates to novel copolymers comprising (per)fluoropolyether chains and functional groups as pendant groups along the backbone of the copolymer.

Description

[Technical Field]

[0001] Cross-reference to related patent applications This application claims priority to European Patent Application No. 22198250.7, filed September 28, 2022, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to novel copolymers comprising (per)fluoropolyether chains and functional groups as pendant groups along the backbone of the copolymer. [Background technology]

[0003] (Per)fluoropolyether polymers (hereinafter referred to as "PFPE polymers") have long been known as additives in base oils or in some lubricating applications.

[0004] Several syntheses of PFPE polymers have been disclosed in the art. The first synthesis of an unspecified perfluorinated polyether mixture was reported in 1953, in which an oily product was obtained during the photo-oligomerization of hexafluoropropene. Since then, many different perfluorinated polyethers have been synthesized and described in the literature.

[0005] U.S. Patent No. 4,500,739 (Montedison) discloses the reaction of peroxidized PFPEs with, among other things, perfluorobutadiene (Group II fluoroolefins). Example 4 discloses the reaction of perfluorobutadiene with a large excess of perfluorinated bisolefins, resulting in pendant unsaturated groups along the polymer chain, so that the reaction can proceed further in the presence of hexamethylenediamine.

[0006] US Pat. No. 8,258,090 (in the name of Solvay Solexis SpA) discloses fluorinated lubricants of the following formula: (I)TO-[AB] z -[A'-B'] z’ -AT During the ceremony, T and T' are C 1~3 Perfluoroalkyl or C 1~6 is alkyl, A and A are perfluoropolyether chains, B is derived from two different olefins, at least one of which has the formula: (Ia)-[(CR1R2-CR3R4) j -(CR5R6-CR7R8) j’ ]- (In the formula, j is 1 to 5, j' is 0 to 4, and the sum of j+j' is 2 to 5, R1 to R8 are halogen, H, C 1~6 (Per)haloalkyl, C 1~6 Alkyl, C 1~6 oxy(per)fluoroalkyl, z is 2 or more, z' is an integer, and the sum of z and z' is such that the number average molecular weight of the polymer of formula (I) is in the range of 500 to 500,000. which are homopolymerizable by a radical route; B' is (Ia), but at least one of R1 to R8 has a different meaning from B.

[0007] This patent discloses block copolymers characterized by a linear backbone without branching: in fact, no branching is obtained within B, which in particular contains (per)fluoropolyether chains.

[0008] PFPE polymers containing functional groups along the backbone have been disclosed in the art and are useful as reactive intermediate compounds and as additives.

[0009] Perfluoropolyether polymers obtained from the reaction of polyperoxide perfluoropolyethers with fluorinated olefins in the presence of ultraviolet radiation are disclosed in US Pat. No. 4,500,739 (Montedison SpA, February 19, 1985).

[0010] U.S. Patent No. 6,403,539 (Ausimont SpA, June 11, 2002) discloses perfluoropolyether polymers containing pendant sulfonyl fluoride groups along the backbone. This patent application discloses a process in which sulfonyl fluoride-containing monomers are simultaneously fed into a liquid reaction medium with an O2 stream, thus obtaining perfluoropolyethers containing peroxide groups within the chain. However, the presence of peroxide groups is undesirable due to safety concerns. Therefore, this patent application discloses subjecting peroxide perfluoropolyethers to thermal treatment, typically at temperatures ranging from 150°C to 250°C, or photochemical treatment, optionally in the presence of a solvent, to obtain non-peroxide products without chain scission. The process disclosed herein, in which functionalized monomers are added at the beginning of polymerization, does not allow for the synthesis of polymers with blocks separated from the functionalized monomers, but rather allows for the synthesis of PFPE polymers with randomly distributed functional groups.

[0011] Multifunctional (per)fluoropolyether polymers are further disclosed in U.S. Pat. Nos. 5,719,259 (EI DuPont de Nemours and Company, February 17, 1998), 4,853,097 (Ausimont Srl, August 1, 1989), and 5,104,911 (Ausimont Srl, April 14, 1992).

[0012] US Patent Application Publication No. 2011 / 0230631 (Solvay Solexis SpA, September 22, 2011) discloses (per)fluoropolyethers comprising at least one (per)fluoropolyoxyalkylene chain containing at least one repeating unit of the formula -CF2-CF(CF2O-SO2F)-O-, where the fluorosulfate group in parentheses is a pendant group that subsequently reacts with a nucleophile to provide functional groups such as carboxylic acids, acyl fluorides, amides, and esters, among others.

[0013] Chinese Patent No. 103724559 (Zhonghao Chengguang Res Inst Chemical Ind, April 16, 2014) discloses a method for forming a stable perfluoropolyether compound by placing perfluoropolyether peroxide prepared by photooxidation in an inert fluorine-containing solvent, introducing perfluoroolefin under ultraviolet irradiation, and reacting the perfluoroolefin with the peroxide.

[0014] WO 2019 / 048394 (Solvay Specialty Polymers Italy SpA, March 14, 2019) discloses polyfunctional perfluoropolyether derivatives containing multiple ionizable groups selected from the group consisting of -SO3Xa, -PO3Xa, and -COOXa, where Xa is H, an ammonium group, or a monovalent metal. Summary of the Invention

[0015] Applicants faced the challenge of providing novel PFPE polymers containing pendant functional groups along the copolymer backbone. Such polymers have low glass transition temperatures (T g ) and is characterized by an increase in viscosity (measured by complex viscosity at 0.1 rad / s at 25° C.) while still remaining in a liquid state at room temperature.

[0016] Additionally, applicant has developed novel PFPE copolymers containing pendant functional groups suitable for use as additives in a variety of technical fields, including rust prevention and antiwear, to enhance compatibility between base oils and thickeners and other components dispersed in such base oils. DETAILED DESCRIPTION OF THE INVENTION

[0017] For purposes of this specification and the claims that follow: the use of parentheses around a symbol or number specifying a formula, such as in a phrase like "polymer (P)", has the sole purpose of better distinguishing the symbol or number from the rest of the text, and therefore said parentheses may be omitted; - the acronym "PFPE" stands for "(per)fluoropolyether" and, when used as a noun, is intended to mean either the singular or the plural, depending on the context; The term "functional groups (F)" is intended to indicate the amount of functional groups in the copolymer according to the invention, as determined, for example, by NMR or titration.

[0018] In a first aspect, the present invention relates to a block copolymer [copolymer (P)] comprising first and second perfluoropolyether chains [PFPE chains], each having two chain ends, wherein the first chain end of each of the first and second PFPE chains is a chain end of the copolymer (P) and each comprises a group selected from a perfluorinated linear or branched alkyl chain containing 1 to 6 carbon atoms, -C(=O)F and -OC(=O)F, and the second chain ends of the first and second PFPE chains are bonded to each other via: at least one first block [block (1)] according to formula (I): -[CR 100 R 101 -CR 102 R 103 ] L^ -(D) L- (I) (In the formula, L^ is an integer between 1 and 250, R 100 , R 101 , R 102 and R 103 are each a halogen atom, more preferably a fluorine or chlorine atom, a linear or branched alkyl chain containing 1 to 6 carbon atoms, -OR 200 are independently selected from R 200 is a linear or branched perfluorinated chain containing 1 to 6 carbon atoms or a group of formula -CF2OR 201 is a group of R 201is a perfluorinated alkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms, or R 100 and R 101 One of the two and R 102 and R 103 is a fluorine atom, and R 100 and R 101 The other and R 102 and R 103 and the other, together form a perhalogenated ring having 4 to 6 members, optionally containing a heteroatom such as an oxygen atom, L is 0 or an integer from 1 to 250, D is a compound of the formula -(CR 100* R 101* -CR 102* R 103* )- group, where (D) is -[CR 100 R 101 -CR 102 R 103 ] L^ -Different from R 100* , R 101* , R 102* and R 103* At least one of the 100 , R 101 , R 102 and R 103 Unlike However, if L̂ and L are not both 0, the repeat units are statistically distributed. at least one second block [block (2)] according to formula (II): [ka] (In the formula, m is an integer from 1 to 5; R5 to R8 are each independently selected from the group consisting of, or preferably including, -F, a perfluorinated straight or branched alkyl chain having 1 to 6 carbon atoms, and a group of formula (III): (III)-R 20 -(X) y During the ceremony, R20 is a sigma bond or a linear or branched perfluoroalkyl chain containing 1 to 12 carbon atoms and preferably containing and / or interrupted by at least one oxygen atom; X is preferably a functional group selected from -SO2F, -SO3H, -COOH, -COF, -CN, -Br and -CONH2, y is an integer of 1 or 2, However, in formula (II), at least one, preferably one of R5 to R8 is a group of formula (III), and optionally at least one third block comprising a PFPE chain [block (3)], However, in copolymer (P): the sum of -(L + L) is at least 1, preferably 1 to 500, even more preferably 2 to 500, more preferably 2 to 300; The total number of blocks (2) is 1 to 100; said at least one block (1), said at least one block (2) and, if present, said at least one block (3) are statistically distributed;

[0019] Advantageously, the copolymer (P) is characterized by a complex viscosity, measured at 0.1 rad / s and 25° C., varying over a wide range, such as from 10 Pa*s to more than 2000 Pa*s. Indeed, an advantage of the method for producing the copolymer (P) according to the invention is that the amounts of the reactants providing each of the blocks (1) and (2) can be adjusted and selected a priori based on the desired properties of the final copolymer (P). This is advantageous, since a priori selection of the amounts of the reactants makes it possible to control and adjust the number of each of the blocks (1) and (2) in the copolymer (P).

[0020] It will be understood by those skilled in the art that the first chain ends of the first and second PFPE chains correspond to two chain ends of copolymer (P).

[0021] Preferably, in the copolymer (P), each of the PFPE chains is a fully fluorinated chain [chain (R f )], wherein the repeat units are independently selected from the group consisting of: (i) -CFXO- (wherein X is -F or -CF3), (ii) -CF₂C₂X₅O₂-, where X, in each occurrence, is the same or different and is -F, or CF₃, provided that at least one of X is -F; (iii) -CF2CF2CF2O-, (iv) -CF2CF2CF2CF2O-, (v)-(CF2) j -CFZ-O- (wherein j is an integer of 0 to 3, and Z is a group represented by the general formula -OR (f-a) -T is a group, and R (f-a) is a fluoropolyoxyalkene chain containing 0 to 10 repeat units, said repeat units being selected from -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, each X is independently F or CF3, and T is a C1 to C3 perfluoroalkylalkyl chain.

[0022] Preferably, the chain (R f ) follows the formula: (R f -I) -[(CFX 1 O) g1 (CFX 2 CFX 3 O) g2 (CF2CF2CF2O) g3 (CF2CF2CF2CF2O) g4 ]- During the ceremony, -X 1 is independently selected from -F and -CF3; -X 2 , X 3are the same or different from each other and, at each occurrence, independently represent -F, -CF3, provided that at least one of X is -F; - g1, g2, g3, and g4 are equal to or different from one another and independently represent integers greater than or equal to 0 such that g1 + g2 + g3 + g4 is in the range of 2 to 300, preferably 2 to 100; when at least two of g1, g2, g3, and g4 are different from zero, the different repeat units are generally statistically distributed along the chain.

[0023] More preferably, the chain (R f ) is the expression: (R f -IIA)-[(CF2CF2O) a1 (CF2O) a2 ]-, (In the formula: a1 and a2 are independently integers equal to or greater than 0 such that the number average molecular weight, as determined by NMR, is between 400 and 100,000, preferably between 400 and 50,000, a1 and a2 being preferably both different from zero, the ratio a1 / a2 being preferably comprised between 0.1 and 10, (R f -IIB)-[(CF2CF2O) b1 (CF2O) b2 (CF(CF3)O) b3 (CF2CF(CF3)O) b4 ]- (In the formula: b1, b2, b3, and b4 are independently integers of 0 or greater such that the number average molecular weight, as determined by NMR, is between 400 and 100,000, preferably between 400 and 50,000, and preferably b1, b2, b3, and b4 are greater than 0; (R f -IIC)-[(CF2CF2O) c1 (CF2O) c2 (CF2(CF2) cw CF2O) c3 ]-, (In the formula: cw=1 or 2, c1, c2, and c3 are independently integers greater than or equal to 0 selected such that the number average molecular weight, as determined by NMR, is 400 to 100,000, preferably 400 to 50,000; preferably, c1, c2, and c3 are all greater than 0, and the ratio c3 / (c1+c2) is generally less than 0.2. The chain is selected from:

[0024] Even more preferably, the chain (R f ) is herein defined as follows: f -III) according to: (R f -III)-[(CFCFO) a1 (CF2O) a2 ]- During the ceremony, - a1 and a2 are integers greater than 0 such that the number average molecular weight, as determined by NMR, is 400 to 100,000, preferably 400 to 50,000, and the ratio a1 / a2 is generally 0.1 to 10, more preferably 0.2 to 5.

[0025] Preferably, in block (1), both L̂ and L are different from 0.

[0026] Preferably, R 100 , R 101 , R 102 and R 103 are each independently a halogen atom such as a fluorine atom or a chlorine atom.

[0027] Preferably, in block (2), m is an integer of 1 to 2.

[0028] Preferably, in block (2), at least one of R5 to R8 is a group of formula (III).

[0029] Preferably, in block (2), R 20 is a sigma bond or a bond of the formula (R 20 -i)~(R 20 -iv) is a group selected from: (R 20 -i) -(CF2) s1 -O-(CF2) s2 - (wherein s1 and s2 each independently represent an integer of 1 to 6, preferably 1 to 3), (R 20 -ii) -O-(CF2) s3 - (wherein s3 is an integer of 1 to 6, preferably 1 to 5), (R 20 -iii) -OR 400 -OR 401 - (In the formula, R 400 is a linear or branched perfluorinated alkyl chain containing 1 to 6, preferably 1 to 3 carbon atoms, more preferably according to the formula -CF-, -CFCF-, -CFCFCF-, -CFCF(CF)-, R401 is a linear or branched perfluorinated alkyl chain containing 1 to 3 carbon atoms, more preferably according to the formula -CF2-, -CF2CF2-, -CF(CF2)-), (R 20 -iv) [ka] (In the formula, R 500 is a linear perfluorinated alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, optionally interrupted by at least one oxygen atom; R 501 is an expression -OR 503 where R 503 is a linear perfluorinated alkyl chain containing 1 to 3 carbon atoms, R 502 is a linear perfluorinated alkyl chain containing 1 to 4 carbon atoms, optionally interrupted by at least one oxygen atom; R 501 and R 502each of which binds a group X as defined above).

[0030] In a second aspect, the present invention relates to a method for producing a copolymer (P) as defined above [Method (P)]. The process according to the invention can be easily scaled up from laboratory scale to pilot scale and industrial scale.

[0031] Advantageously, the copolymer (P) of the invention can be prepared by at least the following steps: (a) at least one perfluoropolyether polymer [PFPE-peroxy] containing at least one peroxide group, -Formula (Xp): [ka] (In the formula, R 21 ~R 23 each is independently -F or a perfluorinated straight or branched alkyl chain having 1 to 6 carbon atoms; R 20 , X, and y are as defined above for formula (III). at least one perfluorinated compound of and at least one compound [compound (O)], (i) fully halogenated olefins containing 2 to 15 carbon atoms; (ii) CF2 = CFOR f (In the formula, R f is a C1-C6 (per)fluoroalkyl group, preferably -CF3, -C2F5, -C3F7, a group C1-C containing a catenary oxygen atom 12 [(per)fluoro]-oxyalkyl, preferably perfluoro-2-propoxypropyl group), (iii) CF2 = CFOCF2OR f2 (In the formula, R f2is selected from the group consisting of C1-C6 perfluoro-alkyl, C5-C6 cyclic perfluoro-alkyl, and C2-C6 perfluoro-oxy-alkyl, containing at least one catenary oxygen atom, preferably R f2 is -CF2CF3, -CF2CF2OCF3, or -CF3), (iv)CF2=CFCF2OR f7 (In the formula, R f7 is selected from the group consisting of C1-C6 perfluoro-alkyl, C5-C6 cyclic perfluoro-alkyl, and C2-C6 perfluoro-oxy-alkyl, each containing at least one catenary oxygen atom; (v) Formula: [ka] (In the formula, R f3 , R f4 , R f5 , R f6 are equal to or different from one another and are independently selected from the group consisting of C1-C6 perfluoroalkyl groups containing fluorine atoms and optionally one or more oxygen atoms, in particular -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3, etc. Perfluorodioxole having contacting at least one compound [compound (O)], preferably selected from the group consisting of: (b) prepared via a process (P) comprising reacting said PFPE peroxy, said at least one compound of formula (Xp) and said at least one compound (O) in the presence of UV radiation or under heat.

[0032] In step (a), the order in which the reactants are added is not limited, and therefore, the PFPE peroxy, the compound of formula (Xp), and the compound (O) can be added to the reaction environment in any order.

[0033] Prior to step (a), the PFPE peroxy can be subjected to partial reduction of the peroxide bond, for example, by chemical reduction or UV or heat treatment.

[0034] Preferably, the PFPE peroxy is a peroxide perfluoropolyether polymer having two chain ends each containing a group selected from a linear or branched perfluorinated alkyl chain containing 1 to 6 carbon atoms or -C(=O)F, and the two chain ends comprise, or preferably consist of, a perfluoropolyether chain [chain (R°)] independently selected from the group consisting of formulas (i) to (v) as defined above. f )] and has a peroxide content (PO), defined as grams of active oxygen in 100 g of PFPE peroxy (Mw=16), between 0.1 and 4, preferably between 0.1 and 3.5.

[0035] Preferably, in the PFPE peroxy, the chain (R f ) conforms to the formula (Rf-I), or (Rf-IIA), (Rf-IIB), (Rf-IIC), or (Rf-III), as defined above.

[0036] According to a preferred embodiment, step (a) of the method of the invention is carried out with at least one compound (O).

[0037] Preferably, said at least one compound (O) is (i) It is preferably selected from the group consisting of fully halogenated olefins containing 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms. More preferably, it is selected from the group consisting of tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE). TFE and HFP are particularly preferred.

[0038] When two or more compounds (O) are used, preferably the first compound (O) is selected from those defined in (I) above and the second compound (O) is (ii) CF2 = CFOR f (In the formula, R f is a C1-C6 (per)fluoroalkyl group, preferably -CF3, -C2F5, -C3F7, a group C1-C containing a catenary oxygen atom 12 [(per)fluoro]-oxyalkyl, preferably perfluoro-2-propoxypropyl group), (iii) CF2 = CFOCF2OR f2 (In the formula, R f2 is selected from the group consisting of C1-C6 perfluoro-alkyl, C5-C6 cyclic perfluoro-alkyl, and C2-C6 perfluoro-oxy-alkyl, containing at least one catenary oxygen atom, preferably R f2 is -CF2CF3, -CF2CF2OCF3, or -CF3), (iv)CF2=CFCF2OR f7 (In the formula, R f7 is selected from the group consisting of C1-C6 perfluoro-alkyl, C5-C6 cyclic perfluoro-alkyl, and C2-C6 perfluoro-oxy-alkyl, each containing at least one catenary oxygen atom; (v) Formula: [ka] (In the formula, R f3 , R f4 , R f5 , R f6 are equal to or different from one another and are independently selected from the group consisting of C1-C6 perfluoroalkyl groups containing fluorine atoms and optionally one or more oxygen atoms, in particular -CF3, -C2F5, -C3F7, -OCF3, -OCF2CF2OCF3, etc. Perfluorodioxole having and preferably selected from the group consisting of:

[0039] Preferably, in said at least one compound of formula (Xp), R 21 , R 22 and R 23 Each of the is -F.

[0040] Preferably, in the compound (Xp), R 20 is a sigma bond or a group of the formula: (R 20 -i)-(CF2) s1 -O-(CF2) s2 - (wherein s1 and s2 each independently represent an integer of 1 to 6, preferably 1 to 3), (R 20 -ii) -O-(CF2) s3 - (wherein s3 is an integer of 1 to 6, preferably 1 to 5), (R 20 -iii)-OR 400 -OR 401 - (In the formula, R 400 is a linear or branched perfluorinated alkyl chain containing 1 to 6, preferably 1 to 3 carbon atoms, more preferably according to the formula -CF-, -CFCF-, -CFCFCF-, -CFCF(CF)-, R401 is a linear or branched perfluorinated alkyl chain containing 1 to 3 carbon atoms, more preferably according to the formula -CF2-, -CF2CF2-, -CF(CF2)-), (R 20 -iv) [ka] (In the formula, R 500 is a linear perfluorinated alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, optionally interrupted by at least one oxygen atom; R 501 is an expression -OR 503 where R 503is a linear perfluorinated alkyl chain containing 1 to 3 carbon atoms, R 502 is a linear perfluorinated alkyl chain containing 1 to 4 carbon atoms, optionally interrupted by at least one oxygen atom; R 501 and R 502 each of which binds a group X as defined above).

[0041] According to a particularly preferred embodiment, said at least one compound of formula (Xp) is selected from: CF2=CFCF2OCF2CF2COOH CF2=CFOCF2COOH CF2=CFO(CF2)5COOH CF2=CFOCF2CF2OCF2COOH CF2=CFOCF2CF2COOH CF2=CFCF2OCF2CF2COF CF2=CFOCF2COF CF2 = CFO(CF2)3OCF(CF3)COF CF2=CFO(CF2)5COF CF2=CFOCF2CF(CF3)OCF2CF2CN CF2=CFOCF2CN CF2=CFO(CF2)5CN CF2 = CFO(CF2)3OCF(CF3)CN CF2=CFCF2OCF2CF2CN CF2=CFOCF2CF2Br CF2=CFCF2OCF2CF2Br CF2=CFOCF2CF(CF3)OCF2CF2Br CF2=CFCF2OCF2CF2CONH2 CF2=CFOCF2CONH2 CF2=CFOCF2CF2CONH2 CF2=CFOCF2CF2SO2F CF2=CFSO2F CF2=CFOCF2CF(SO2F)2 CF2=CFOCF2CF(CF2OCF2CF2SO2F)(OCF2CF2SO2F) CF2=CFOCF2CF(CF2CF2SO2F)(OCF2CF2SO2F) CF2=CFOCF2OCF2CF(CF2OCF2CF2SO2F)(SO2F)

[0042] Some exemplary compounds of formula (Xp) and their preparation are provided in WO 03 / 106515 (Daikin Ind.), JP 2017-025242 (ASAHI GLASS CO., LTD.), and U.S. Patent Application Publication No. 2008 / 138685 (AGC Inc.).

[0043] The amount of each of the at least one compound (Xp) and the compound (O) is not limited.

[0044] For example, the ratio of the equivalents of the double bonds of the compound (Xp) to the equivalents of the peroxide groups can be in the range of 1:100 to 5000:100.

[0045] Step (a) of process (P) can be advantageously carried out by contacting said PFPE peroxy with a compound of one of formula (Xp).

[0046] Alternatively, step (a) can be carried out by contacting the PFPE peroxy with two or more compounds of formula (Xp).

[0047] Steps (a) and (b) can be carried out in the presence of a fluorinated solvent, preferably selected from the group consisting of perfluorocarbons, hydrofluorocarbons, perfluoropolyethers, and hydrofluoropolyethers.

[0048] Preferably, step (b) is carried out in the presence of UV radiation for a period of 2 to 150 hours, preferably 5 to 100 hours.

[0049] Preferably, step (b) is carried out at a temperature of from −60° C. to +150° C., more preferably from −20° C. to +100° C., even more preferably from 0° C. to 60° C., in the presence of UV radiation.

[0050] Alternatively, step (b) can be carried out under heat treatment, preferably by heating at a temperature of 150°C to 250°C.

[0051] Preferably, step (b) is carried out in an inert atmosphere.

[0052] In a third aspect, the present invention relates to a copolymer (P) obtainable via the process (P) described above.

[0053] Advantageously, the functional groups introduced as pendant groups in block (2) of copolymer (P), such as, in particular, -SO2F, -SO3H, -COOH, -COF, -CN, -Br, and -CONH2, and the functional groups at the chain ends of copolymer (P), such as, in particular, -COF and -OC(O)F, can be appropriately reacted to give other different functional groups.

[0054] The expression "capable of reacting" is intended to indicate that such functional groups can be subjected to, for example, salification, hydrolysis, reduction, oxidation, or a different chemical reaction to provide functional groups with the desired reactivity, taking into account the end use of the copolymer (P).

[0055] Advantageously, the functionalized copolymer according to the invention [copolymer (P F )] is obtained from the above method (P), which further comprises, after step (b), at least one step (c) comprising at least one of salification, hydrolysis, oxidation, reduction or another chemical reaction capable of providing the desired functional group.

[0056] The present invention further relates to the copolymer (P) obtained at the end of step (c) of the method (P). F ) is included.

[0057] Therefore, the present invention provides a block copolymer [copolymer (P F ) wherein the first chain end of each of the first and second PFPE chains is a chain end of a copolymer (P), each of which is a perfluorinated linear or branched alkyl chain containing 1 to 6 carbon atoms, —COOH, and an organic cation, preferably an onium cation, more preferably ammonium, or an inorganic cation, preferably an alkali metal cation, more preferably Na + , K. + their salts with; -COOR (wherein R is a linear or branched alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 carbon atom); -COF; -CONH; -CON(R 300 )(R 301 )(wherein, R 300 and R 301 each of which has the same meaning as defined for R);-(R) c -OH, where c is 0 or 1 and R is as defined above; -C(O)-OC(O)R, where R is as defined above, provided that (i) at least one chain end of the first and second PFPE chains contains a group other than a perfluorinated linear or branched alkyl chain having 1 to 6 carbon atoms, and (ii) when one chain end contains the group -COF, the other chain end does not contain a perfluorinated linear or branched alkyl chain having 1 to 6 carbon atoms or -COF; the second chain ends of the first and second PFPE chains are linked to each other via: at least one first block [block (1)] according to formula (I): -[CR 100 R 101 -CR 102 R 103 ] L^ -(D) L- (I) (In the formula, L^, L, D, R100 , R 101 , R 102 and R 103 has the meaning defined above), at least one second block [block (2)] according to formula (II): [ka] (In the formula, m, R5 to R8 have the meanings defined above), and optionally at least one third block comprising a PFPE chain [block (3)], However, copolymer (P F ) inside, The sum of -(L+L^) is 1 to 500, more preferably 2 to 500, and more preferably 2 to 300; The total number of blocks (2) is 1 to 100; said at least one block (1), said at least one block (2) and, if present, said at least one block (3) are statistically distributed;

[0058] In a further aspect, the present invention provides a copolymer of two or more copolymers (P F ), mixture [mixture (P F )].

[0059] A purification step may be carried out after any of steps (b), (c) and / or (d) of the method (P), but typically after the copolymer (P) or copolymer (P) according to the invention. F ) mixture is obtained.

[0060] Therefore, in a further aspect, the present invention relates to a mixture [mixture (P)] comprising two or more copolymers (P) as defined above.

[0061] It will be clear to those skilled in the art that the mixture (P) can be obtained via the above method (P).

[0062] Advantageously, said mixture (P) can be subjected to one or more purification steps (also called "fractionation" steps), thus 19 Distinct copolymers (P) can be obtained, characterized by different viscosities and / or number average molecular weights, measured by F-NMR, and / or functionality (F), preferably between 3 and 102.

[0063] The mixture may further contain PFPE peroxy used as starting material and / or a mixture of copolymers (P) containing peroxy groups [copolymer (P O-O )], and / or copolymers containing peroxy groups (P F ) mixture [copolymer (P F-O-O )] can be obtained.

[0064] Advantageously, the copolymer (P O-O ), and / or copolymers (P F-O-O ) can be isolated and used as an intermediate in other processes.

[0065] The copolymer (P) of the present invention or the copolymer (P F The amount of peroxy groups that may be present in a mixture containing PFPE peroxy can be up to 99% based on the amount of starting peroxy groups in the PFPE peroxy, but depending on the end use, the amount of peroxy groups can be appropriately adjusted, for example, to 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5%.

[0066] More preferably, the amount of peroxy groups is at most 1.0, even more preferably at most 0.5%, and even more preferably at most 0.1%.

[0067] In another aspect, the present invention provides a block copolymer [copolymer (P O-O wherein each of the first and second PFPE chains is a chain (Rf) as defined above, or O-O), where (Rf O-O ) is a repeating unit having a peroxide content (PO), defined as grams of active oxygen in 100 g of PFPE peroxy (Mw=16), of between 0.1 and 4, preferably between 0.1 and 3.5, according to any one of formulas (i) to (v), as defined above for (R°), wherein each of the first and second PFPE chains has two chain ends, the first chain ends of each of the first and second PFPE chains are chain ends of a copolymer (P) each comprising a group selected from a perfluorinated linear or branched alkyl chain containing 1 to 6 carbon atoms, —C(═O)F and —OC(═O)F, and the second chain ends of the first and second PFPE chains are bonded to each other via: at least one first block [block (1)] according to formula (I) as defined above, at least one second block [block (2)] according to formula (II) as defined above, and - optionally at least one third block [block (3)] comprising a PFPE chain as defined above, however, *Copolymer (P O-O ) inside, - the blocks (1), (2) and, if present, the at least one block (3) are statistically distributed, The sum of -(L + L) is at least 1, preferably 1 to 500, more preferably 2 to 500, more preferably 2 to 300; -The total number of blocks (2) is 1 to 100.

[0068] In yet another embodiment, the present invention provides a block copolymer [copolymer (P F-O-O )], wherein each of the first and second PFPE chains is a chain (Rf) as defined above, or a chain (Rf O-O ), where (Rf O-O) is a repeating unit having a peroxide content (PO), defined as grams of active oxygen in 100 g of PFPE peroxy (Mw=16), of between 0.1 and 4, preferably between 0.1 and 3.5, according to any one of formulas (i) to (v), as defined above for (R°), wherein each of the first and second PFPE chains has two chain ends, the first chain end of each of the first and second PFPE chains being a chain end of a copolymer (P), each of which is a perfluorinated linear or branched alkyl chain containing 1 to 6 carbon atoms, —COOH, and an organic cation, preferably an onium cation, more preferably ammonium, or an inorganic cation, preferably an alkali metal, more preferably Na + , K. + their salts with; -COOR (wherein R is as defined above); -COF; -CON(R 300 )(R 301 )(wherein, R 300 and R 301 each of which is a hydrogen atom or has the same meaning as defined for R);-(R) c -OH (wherein c is 0 or 1 and R is as defined above); -C(O)-OC(O)R (wherein R is as defined above); -Br; -CN; and the second chain ends of the first and second PFPE chains are bonded to each other via: at least one first block [block (1)] according to formula (I) as defined above, at least one second block [block (2)] according to formula (II) as defined above, and - optionally at least one third block [block (3)] comprising a PFPE chain as defined above, however, *Copolymer (P F-O-O ) inside, - the blocks (1), (2) and, if present, the at least one block (3) are statistically distributed, The sum of -(L + L) is at least 1, preferably 1 to 500, more preferably 2 to 500, more preferably 2 to 300; -The total number of blocks (2) is 1 to 100.

[0069] In yet another aspect, the present invention relates to a method for producing a polymerizable composition comprising at least one copolymer (P) as defined above and at least one of the PFPE peroxys used as starting materials and / or a polymerizable composition comprising at least one copolymer (P) as defined above. O-O and one or more of the following:

[0070] In yet another aspect, the present invention provides a polymerizable composition comprising at least one copolymer (P F ) and at least one of the copolymers (P) defined above, and the PFPE peroxy used as starting material and the one or more copolymers (P O-O ) and / or one or more of said copolymers (P) as defined above F-O-O ) and the mixture [Mixture (M2)].

[0071] The copolymer (P) and / or copolymer (P F ) can be used for various applications in several industries where excellent resistance and durability at high temperatures and in harsh environments are required. For example, copolymer (P) and / or copolymer (P F ) can be used as a base oil for lubricants. Alternatively, copolymer (P) and / or copolymer (P F ) can be used as an additive in halogenated oils and / or greases.

[0072] To this end, advantageously, the copolymers according to the invention as well as the mixtures described herein are in the liquid state at room temperature or even below room temperature, which offers advantages in handling and storage of the copolymers.

[0073] Advantageously, therefore, the copolymer (P) is in the liquid state at room temperature.

[0074] Also advantageously, copolymers (P F ) is in a liquid state at room temperature.

[0075] Furthermore, copolymer (P O-O ) and copolymer (P F-O-O ), and each of the mixtures (M1) and (M2) are in a liquid state at room temperature.

[0076] The copolymer (P) and / or copolymer (P F ) is suitable for use as an additive in a variety of technical fields, including rust prevention, antiwear, to enhance compatibility between base oils and thickeners and other components dispersed in such base oils.

[0077] To the extent that the disclosure of any patents, patent applications, and publications incorporated herein by reference contradicts the statements of this application to the extent that a term may be unclear, the statements of this application shall control.

[0078] The present invention is exemplified herein below in more detail by the examples contained in the experimental section below, which are illustrative only and should not be construed as limiting the scope of the invention in any way. [Example]

[0079] Experimental section material The peroxide perfluoropolyether oil was obtained from Solvay Specialty Polymers Italy SpA and conforms to the following formula: XO-(CF2CF2O) a1 (CF2O) a2 (O) h -X' During the ceremony, X and X' are -CF3, -CF2COF, -COF and have the following properties: Mn=31 990 g / mol; PO=1.61%; m / n=1.0.

[0080] The following were purchased by Anles LTD and used as is: Perfluorovinylcyano(8CNVE)CF2=CFOCF2CF(CF3)OCF2CF2CN

[0081] The perfluorinated solvents Galden® HT200 and Galden® D100, as well as tetrafluoroethylene (TFE) and perfluoromethyl vinyl ether (PMVE), and perfluorosulfonyl vinyl ether (VEFS) CF2=CFOCF2CF2SO2F were obtained from Solvay Specialty Polymers Italy SpA.

[0082] method 19 It worked for F nuclides 19 F-NMR—Varian Mercury 300 MHz spectrometer was used to obtain the structure, molecular weight, chain end composition and functionality of the perfluoropolyether oils. 19 F-NMR spectra were obtained on pure samples using CFCl3 as an internal standard.

[0083] The peroxide content (PO) is expressed as grams of peroxide oxygen per 100 g of polymer. Analysis of the peroxide content was performed by iodometric titration using a Mettler DL40 apparatus equipped with a platinum electrode. The sensitivity limit for the PO determination was 0.0002%.

[0084] FT-IR spectra were acquired on a Thermo Fisher IS10 spectrometer on liquid samples as thin films on KBr.

[0085] Complex viscosity was measured by frequency sweep testing using an MCR502 Anton-Paar rheometer (25 mm diameter) in parallel plate geometry. Viscosity was measured in this manner at 25°C and 100°C, and values ​​are reported at an oscillation of 0.1 rad / s.

[0086] Example 1a - Preparation of PFPE Copolymer with TFE, MVE and VEFS 251 g of the above-described peroxide perfluoropolyether oil was charged into a 1500 mL stirred cylindrical photochemical reactor equipped with a high-pressure mercury lamp (Model HANAU TQ150), a thermocouple, a condenser, and a mechanical stirrer. The oil was diluted with 1876 g of perfluorinated solvent, Galden HT200, and 14.0 g of VEFS. The mixture was then purged with nitrogen under stirring, after which two fluorinated olefins, PMVE and TFE, were introduced into the reactor at rates of 14.6 and 8.0 g / h, respectively. After the flow was initiated, the UV lamp was turned on and the reaction was carried out at 20°C for 7 hours. The olefin flow was then interrupted and the UV lamp was turned off.

[0087] The resulting solution was distilled in a round-bottom flask equipped with a magnetic stirrer at 240°C for 4 hours to remove the solvent and traces of unreacted monomers. Distillation was carried out first at atmospheric pressure and then under reduced pressure (0.1 mbar) until complete removal of the solvent.

[0088] 275.1 g of copolymer in the form of a clear viscous oil was obtained as residue, which was analyzed by iodometric titration to confirm complete removal of the peroxide units.

[0089] Product 19 F-NMR analysis confirmed the absence of residual peroxides.

[0090] The incorporation of VEFS, TFE and PMVE in the copolymer was at concentrations of 3.8, 13.4 and 9.6 wt %, respectively.

[0091] 19 F-NMR analysis confirmed the following structure: XO-(CF2CF2O) a1 (CF2O) a2 [CF2CFO(CF2CF2SO2F)] m (CF2CF2) L^ -[CF2CF(OCF3)] L -X' During the ceremony, a1 / a2=0.9, m=3.8, L^=47.8, L=20.6 (all values ​​are averages and are statistically distributed), X and X' = -CF3, -CF2COF and -OCOF, Number average molecular weight (M n )=35600 g / mol.

[0092] Example 1b - Preparation of PFPE Copolymer Containing TFE, MVE, and VEFS The polymer was prepared following the same procedure as disclosed in Example 1 above, except that 23.3 g of VEFS was provided.

[0093] 279.9 g of copolymer in the form of a clear viscous oil was obtained as residue, which was analyzed by iodometric titration to confirm complete removal of the peroxide units.

[0094] Product 19 F-NMR analysis confirmed the absence of residual peroxides.

[0095] The incorporation of VEFS, TFE and PMVE in the copolymer was at concentrations of 5.0, 12.7 and 11.4 wt %, respectively.

[0096] 19 F-NMR analysis confirmed the following structure: XO-(CF2CF2O) a1 (CF2O) a2 [CF2CFO(CF2CF2SO2F)] m (CF2CF2) L^ -[CF2CF(OCF3)] L -X' During the ceremony, a1 / a2=1.0, m=6.8, L^=48.9, L=26.5 (all values ​​are averages, blocks are statistically distributed), X and X' = -CF3, -CF2COF and -OCOF, Number average molecular weight (M n )=38500 g / mol.

[0097] Comparative Example 1 - Preparation of PFPE Copolymer with VEFS 250.5 g of the above-described peroxide perfluoropolyether oil was charged into the same reactor as in Example 1. The oil was diluted with 1875 g of a perfluorinated solvent, Galden HT200. Next, 14.0 g of VEFS was added to the reactor, and the mixture was purged with nitrogen. The UV lamp was then turned on, and the reaction was carried out at 20°C for 7 hours. After that, the UV lamp was turned off.

[0098] The resulting solution was distilled in a round-bottom flask equipped with a magnetic stirrer at 240°C for 4 hours to remove the solvent and traces of unreacted monomers. Distillation was carried out first at atmospheric pressure and then under reduced pressure (0.1 mbar) until complete removal of the solvent.

[0099] 215.9 g of copolymer in the form of a clear oil was obtained as residue, which was analyzed by iodometric titration to confirm complete removal of the peroxide units.

[0100] The VEFS concentration in the copolymer was 6.0 wt %.

[0101] Product 19 F-NMR analysis confirmed the absence of residual peroxide and the following structure: XO-(CF2CF2O) a1 (CF2O) a2 (CF2CFO(CF2CF2SO2F)) m -X' In the formula, a1 / a2=1.0, m = 5.6 on average, X and X' = -CF3, -CF2COF and -OCOF, Number average molecular weight (Mn) = 30400 g / mol.

[0102] Example 2 - Preparation of PFPE Copolymer with TFE, MVE and 8CNVE 250 g of the above-described peroxide perfluoropolyether oil was charged to the same reactor as in Example 1. The oil was diluted with 1875 g of perfluorinated solvent, Galden D100, and 29.2 g of 8CNVE were added to the reactor.

[0103] The mixture was then purged with nitrogen under stirring, after which two fluorinated olefins, PMVE and TFE, were introduced into the reactor at rates of 17.1 and 9.3 g / h, respectively. After the flows were initiated, the UV lamp was turned on and the reaction was carried out for 6 hours at 20° C. The olefin flow was then discontinued and the UV lamp was left on for an additional 35 hours at 20° C.

[0104] After a total of 35 hours of UV irradiation, the lamp was switched off and the reaction mixture was transferred to a 2 L round-bottom flask and stripped at 120°C under reduced pressure (0.1 mbar) for 6 hours until the solvent and traces of unreacted monomer were completely removed.

[0105] 265 g of copolymer in the form of a clear viscous oil was obtained as residue.

[0106] The incorporation of 8CNVE, TFE, and PMVE into the copolymer was found to be at concentrations of 7.3, 12.0, and 11.4 wt%, respectively. The introduction of -CN functional groups was also confirmed by FT-IR spectroscopy, which showed a peak at 2269 cm -1 The presence of a peak was confirmed.

[0107] Product 19 F-NMR analysis confirmed the copolymer structure: XO-(CF2CF2O) a1 (CF2O) a2 -(CF2CFO(CF2CF(CF3)OCF2CF2CN)) m (CF2CF2) L^ - (CF2CF(OCF3)) L -X' During the ceremony, a1 / a2=0.9, m = 6.6, L^ = 42.0, L = 24.0 (all values ​​are averages, repeat units are statistically distributed), X and X' = -CF3, -CF2COF and -OCOF, Number average molecular weight (Mn) = 35000 g / mol.

[0108] Comparative Example 2-8 Preparation of PFPE Copolymer with CNVE 252.1 g of the above-described peroxide perfluoropolyether oil was charged into the same reactor as in Example 1. The oil was diluted with 1873 g of a perfluorinated solvent, Galden HT200. Next, 19.45 g of 8CNVE was added to the reactor, and the mixture was purged with nitrogen. The mixture was then purged with nitrogen under stirring, and the UV lamp was turned on at 20°C for 41 hours.

[0109] After this time, the lamp was switched off and the reaction mixture was transferred to a 2 L round-bottom flask. The mixture was stripped at 120° C. under reduced pressure (0.1 mbar) for 6 hours.

[0110] 224.5 g of copolymer in the form of a clear viscous oil was obtained as residue.

[0111] The introduction of the –CN functional group was also confirmed by FT-IR spectroscopy, which showed a peak at 2269 cm -1 The presence of a peak was confirmed.

[0112] The incorporation of 8CNVE into the copolymer was at a concentration of 8.0%.

[0113] Product 19 F-NMR analysis confirmed the copolymer structure: XO-(CF2CF2O) a1 (CF2O) a2 -(CF2CFO(CF2CF(CF3)OCF2CF2CN)) m -X' During the ceremony, a1 / a2=0.9, m=6.4, X and X' = -CF3, -CF2COF and -OCOF, Number average molecular weight (M n ) = 31100 g / mol.

[0114] The properties of the copolymers according to the invention and the comparative examples are summarized in Table 1 below.

[0115] [Table 1]

[0116] The above data showed that in the copolymers according to the invention, the complex viscosity increased by an order of magnitude while the molecular weight remained the same.

Claims

1. A block copolymer [copolymer (P)] comprising first and second perfluoropolyether chains [PFPE chains], each having two chain ends, wherein the first chain ends of each of the first and second PFPE chains are chain ends of the copolymer (P), each comprising a group selected from a perfluorinated linear or branched alkyl chain containing 1 to 6 carbon atoms, -C(=O)F and -OC(=O)F, and the second chain ends of the first and second PFPE chains are bonded to each other via: at least one first block [block (1)] according to formula (I): -[CR １００ R １０１ -CR １０２ R １０３ ] Ｌ＾ -(D) Ｌ－ (I) (In the formula, L^ is an integer from 1 to 250, R １００ , R １０１ , R １０２ and R １０３ are each a halogen atom, more preferably a fluorine or chlorine atom, a linear or branched alkyl chain containing 1 to 6 carbon atoms, -OR ２００ and R ２００ is a linear or branched perfluorinated chain containing 1 to 6 carbon atoms or of the formula -CF ２ OR ２０１ is a group of R ２０１ is a perfluorinated alkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms, or R １００ and R １０１ One of the two and R １０２ and R １０３ is a fluorine atom, and R １００ and R １０１ The other and R １０２ and R １０３ together form a perhalogenated ring having 4 to 6 members, optionally containing a heteroatom such as an oxygen atom, L is 0 or an integer from 1 to 250, D is a group of the formula -(CR １００＊ R １０１＊ -CR １０２＊ R １０３＊ )—, where (D) is —[CR １００ R １０１ -CR １０２ R １０３ ] Ｌ＾ Unlike -, R １００＊ , R １０１＊ , R １０２＊ and R １０３＊ At least one of １００ , R １０１ , R １０２ and R １０３ Unlike provided that if L^ and L are not both 0, the repeat units are statistically distributed. at least one second block [block (2)] according to formula (II): 【Chemistry 1】 (In the formula, m is an integer from 1 to 5, R ５ ~R ８ are each independently selected from the group consisting of, or preferably including, -F, a perfluorinated straight or branched alkyl chain having 1 to 6 carbon atoms, and a group of formula (III): (_). ２０ ()) ｙ During the ceremony, R ２０ is a sigma bond or a linear or branched perfluoroalkyl chain containing 1 to 12 carbon atoms and preferably containing and / or interrupted by at least one oxygen atom; X is preferably —SO ２ F, -SO ３ H, —COOH, —COF, —CN, —Br, and —CONH ２ is a functional group selected from y is an integer of 1 or 2; However, in formula (II), R ５ ~R ８ at least one, preferably one, of the formula (III) is a group and - optionally at least one third block [block (3)] comprising a PFPE chain, However, in the copolymer (P): the sum of -(L + L^) is at least 1, preferably 1 to 500, more preferably 2 to 500, more preferably 2 to 300; - the total number of blocks (2) is between 1 and 100; - a block copolymer [copolymer (P)] in which said at least one block (1), said at least one block (2) and, if present, said at least one block (3) are statistically distributed.

2. Each of said PFPE chains is a fully fluorinated chain [chain (R ｆ ) ], wherein the repeating unit is: (i) -CFXO- (wherein X is -F or -CF ３ (which is (ii) -CFXCFXO-, where X in each occurrence is the same or different and is -F, or -CF ３ with the proviso that at least one of X is -F), (iii)-CF ２ CF ２ CF ２ O-、 (iv)-CF ２ CF ２ CF ２ CF ２ O-、 (v)-(CF ２ ) ｊ -CFZ-O- (where j is an integer from 0 to 3, and Z is a group of the general formula -O-R （ｆ－ａ） -T group, and R （ｆ－ａ） is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, and the repeating units are -CFXO-, -CF ２ CFXO-, -CF ２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ CF ２ and each X is selected from -F, or -CF ３ and T is C １ ~C ３ perfluoroalkyl alkyl chain) The copolymer (P) according to claim 1, independently selected from the group consisting of:

3. In the block (1): -L^ and L are both different from 0, and / or -R １００ , R １０１ , R １０２ and R １０３ and each independently represent a halogen atom, preferably selected from fluorine and chlorine atoms.

4. In the block (2): -m is an integer from 1 to 2, and / or -R ５ ~R ８ is a group of formula (III), and / or -R ２０ is a sigma bond or has the formula (R ２０ -i) to (R ２０ -iv): (R ２０ -i) -(CF ２ ) ｓ１ -O-(CF ２ ) ｓ２ - (wherein s1 and s2 each independently represent an integer of 1 to 6, preferably 1 to 3); () ２０ )) -O-(CF ２ ) ｓ３ - (wherein s3 is an integer of 1 to 6, preferably 1 to 5); () ２０ )) -O-R ４００ -O-R ４０１ - (In the formula, R ４００ contains 1 to 6, preferably 1 to 3 carbon atoms, and more preferably has the formula -CF ２ -, -CF ２ CF ２ -, -CF ２ CF ２ CF ２ -, -CF ２ CF (CF ３ )--a linear or branched perfluorinated alkyl chain, R401 contains 1 to 3 carbon atoms, more preferably a group of formula -CF ２ -, -CF ２ CF ２ -, -CF(CF ２ )--a linear or branched perfluorinated alkyl chain, (R) ２０ (-iv) 【Chemistry 2】 (In the formula, R ５００ is a linear perfluorinated alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, optionally interrupted by at least one oxygen atom; R ５０１ is the formula -OR ５０３ where R ５０３ is a linear perfluorinated alkyl chain containing 1 to 3 carbon atoms; R ５０２ is a linear perfluorinated alkyl chain containing 1 to 4 carbon atoms, optionally interrupted by at least one oxygen atom; R ５０１ and R ５０２ Each of the groups (X) according to claim 1 ｙ (combining The copolymer (P) according to any one of claims 1 to 3, wherein the group is selected from the following:

5. A method for producing the copolymer (P) according to any one of claims 1 to 4, comprising the following steps: (a) at least one perfluoropolyether polymer containing at least one peroxide group [PFPE-peroxy], at least one perfluorinated compound of formula (X-p): 【Transformation 3】 (In the formula, R ２１ ~R ２３ each is independently —F or a perfluorinated straight or branched alkyl chain having 1 to 6 carbon atoms; R ２０ is a sigma bond or a linear or branched perfluoroalkyl chain containing 1 to 12 carbon atoms and preferably containing and / or interrupted by at least one oxygen atom; X is preferably —SO ２ F, -SO ３ H, —COOH, —COF, —CN, —Br, and —CONH ２ is a functional group selected from y is an integer of 1 or 2; However, in formula (II), R ５ ~R ８ at least one, preferably one, of the formula (III) and at least one compound [compound (O)], (i) fully halogenated olefins containing 2 to 15 carbon atoms; (ii)CF ２ =CFOR ｆ (In the formula, R ｆ is C １ ~C ６ (Per)fluoroalkyl groups, preferably —CF ３ , -C ２ F ５ , -C ３ F ７ , a group C containing a catenary oxygen atom １ ~C １２ [(per)fluoro]-oxyalkyl, preferably perfluoro-2-propoxypropyl group); (iii)CF ２ =CFOCF ２ OR ｆ２ (In the formula, R ｆ２ C contains at least one catenary oxygen atom １ ~C ６ Perfluoro-alkyl, C ５ ~C ６ Cyclic perfluoro-alkyl, and C ２ ~C ６ perfluoro-oxy-alkyl, preferably R ｆ２ is -CF ２ CF ３ , -CF ２ CF ２ OCF ３ , or -CF ３ (which is (iv)CF ２ =CFCF ２ OR ｆ７ (In the formula, R ｆ７ C contains at least one catenary oxygen atom １ ~C ６ Perfluoro-alkyl, C ５ ~C ６ Cyclic perfluoro-alkyl, and C ２ ~C ６ perfluoro-oxy-alkyl), (v) Formula: 【Chemistry 4】 (In the formula, R ｆ３ , R ｆ４ , R ｆ５ , R ｆ６ are equal to or different from one another and contain a fluorine atom and optionally one or more oxygen atoms, in particular -CF ３ , -C ２ F ５ , -C ３ F ７ , -OCF ３ , -OCF ２ CF ２ OCF ３ C such as １ ~C ６ perfluoroalkyl groups) Perfluorodioxole having contacting at least one compound [compound (O)], preferably selected from the group consisting of: (b) a method of preparation [Method P], comprising the step of reacting said PFPE peroxy, said at least one compound of formula (X-p) and said at least one compound (O) in the presence of UV light or under heating.

6. 6. The method (P) of claim 5, wherein prior to step (a), the PFPE-peroxy is subjected to partial reduction of the peroxide bonds by chemical reduction or UV treatment or heat treatment.

7. The PFPE peroxy is a peroxide perfluoropolyether polymer having two chain ends each containing a group selected from a linear or branched perfluorinated alkyl chain containing 1 to 6 carbon atoms or —C(═O)F, the two chain ends being represented by formulas (i) to (v): (i) -CFXO- (wherein X is -F or -CF ３ (which is (ii) -CFXCFXO-, where X in each occurrence is the same or different and is -F, or -CF ３ with the proviso that at least one of X is -F), (iii)-CF ２ CF ２ CF ２ O-、 (iv)-CF ２ CF ２ CF ２ CF ２ O-、 (v)-(CF ２ ) ｊ -CFZ-O- (where j is an integer from 0 to 3, and Z is a group of the general formula -O-R （ｆ－ａ） -T group, and R （ｆ－ａ） is a fluoropolyoxyalkene chain containing 0 to 10 repeating units, and the repeating units are -CFXO-, -CF ２ CFXO-, -CF ２ CF ２ CF ２ O-, -CF ２ CF ２ CF ２ CF ２ and each X is selected from -F, or -CF ３ and T is C １ ~C ３ perfluoroalkyl alkyl chain) A perfluoropolyether chain [chain (R ｆ 7. The method of claim 5 or 6, wherein the PFPE-peroxyl group is bonded to the other end of a PFPE-peroxyl group, and has a peroxide content (PO), defined as grams of active oxygen in 100 g of PFPE-peroxyl group, of between 0.1 and 4.

8. One compound (O) is used in the method (P), said one compound (O) being The process (P) according to any one of claims 5 to 7, wherein (i) the fully halogenated olefins (P) are selected in the group comprising fully halogenated olefins containing from 2 to 10 carbon atoms, preferably from 2 to 8 carbon atoms.

9. At least two compounds (O) are used in the process (P), The first compound (O) is (i) selected in the group comprising fully halogenated olefins containing 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms; The second compound (O) is (ii)CF ２ =CFOR ｆ (In the formula, R ｆ is C １ ~C ６ (Per)fluoroalkyl groups, preferably —CF ３ , -C ２ F ５ , -C ３ F ７ , a group C containing a catenary oxygen atom １ ~C １２ [(per)fluoro]-oxyalkyl, preferably perfluoro-2-propoxypropyl group); (iii)CF ２ =CFOCF ２ OR ｆ２ (In the formula, R ｆ２ C contains at least one catenary oxygen atom １ ~C ６ Perfluoro-alkyl, C ５ ~C ６ Cyclic perfluoro-alkyl, and C ２ ~C ６ perfluoro-oxy-alkyl, preferably R ｆ２ is -CF ２ CF ３ , -CF ２ CF ２ OCF ３ , or -CF ３ (which is (iv)CF ２ =CFCF ２ OR ｆ７ (In the formula, R ｆ７ C contains at least one catenary oxygen atom １ ~C ６ Perfluoro-alkyl, C ５ ~C ６ Cyclic perfluoro-alkyl, and C ２ ~C ６ perfluoro-oxy-alkyl), (v) Formula: 【Transformation 5】 (In the formula, R ｆ３ , R ｆ４ , R ｆ５ , R ｆ６ are equal to or different from one another and contain a fluorine atom and optionally one or more oxygen atoms, in particular -CF ３ , -C ２ F ５ , -C ３ F ７ , -OCF ３ , -OCF ２ CF ２ OCF ３ C such as １ ~C ６ perfluoroalkyl groups) Perfluorodioxole having The method (P) according to any one of claims 5 to 7, comprising, more preferably selected from the group consisting of:

10. In said at least one compound of formula (X-p), -R ２１ , R ２２ and R ２３ each of is —F, and / or -R ２０ is a sigma bond or has the formula (R ２０ -i) to (R ２０ -iv): (R ２０ -i) -(CF ２ ) ｓ１ -O-(CF ２ ) ｓ２ - (wherein s1 and s2 each independently represent an integer of 1 to 6, preferably 1 to 3); () ２０ )) -O-(CF ２ ) ｓ３ - (wherein s3 is an integer of 1 to 6, preferably 1 to 5); () ２０ )) -O-R ４００ -O-R ４０１ - (In the formula, R ４００ contains 1 to 6, preferably 1 to 3 carbon atoms, and more preferably has the formula -CF ２ -, -CF ２ CF ２ -, -CF ２ CF ２ CF ２ -, -CF ２ CF (CF ３ )--a linear or branched perfluorinated alkyl chain, R401 contains 1 to 3 carbon atoms, more preferably a group of formula -CF ２ -, -CF ２ CF ２ -, -CF(CF ２ )--a linear or branched perfluorinated alkyl chain, (R) ２０ (-iv) 【Transformation 6】 (In the formula, R ５００ is a linear perfluorinated alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, optionally interrupted by at least one oxygen atom; R ５０１ is the formula -OR ５０３ where R ５０３ is a linear perfluorinated alkyl chain containing 1 to 3 carbon atoms; R ５０２ is a linear perfluorinated alkyl chain containing 1 to 4 carbon atoms, optionally interrupted by at least one oxygen atom; R ５０１ and R ５０２ each of which bonds to a group X as defined above The method (P) according to any one of claims 5 to 9, wherein the group is selected from the following:

11. The at least one compound of formula (X-p) has the following formula: CF ２ =CFCF ２ OCF ２ CF ２ COOH CF ２ =CFOCF ２ COOH CF ２ =CFO(CF ２ ) ５ COOH CF ２ =CFOCF ２ CF ２ OCF ２ COOH CF ２ =CFOCF ２ CF ２ COOH CF ２ =CFCF ２ OCF ２ CF ２ COF CF ２ =CFOCF ２ COF CF ２ =CFO(CF ２ ) ３ OCF(CF ３ )COF CF ２ =CFO(CF ２ ) ５ COF CF ２ =CFOCF ２ CF(CF ３ )OCF ２ CF ２ CN CF ２ =CFOCF ２ CN CF ２ =CFO(CF ２ ) ５ CN CF ２ =CFO(CF ２ ) ３ OCF(CF ３ )CN CF ２ =CFCF ２ OCF ２ CF ２ CN CF ２ =CFOCF ２ CF ２ Br CF ２ =CFCF ２ OCF ２ CF ２ Br CF ２ =CFOCF ２ CF(CF ３ )OCF ２ CF ２ Br CF ２ =CFCF ２ OCF ２ CF ２ CONH ２ CF ２ =CFOCF ２ COIN ２ CF ２ =CFOCF ２ CF ２ COIN ２ CF ２ =CFOCF ２ CF ２ SO ２ F CF ２ =CFSO ２ F CF ２ =CFOCF ２ CF(SO ２ F) ２ CF ２ =CFOCF ２ CF(CF ２ OCF2CF2SO ２ F)(OCF ２ CF ２ SO ２ F) CF ２ =CFOCF ２ CF(CF ２ CF ２ SO ２ F)(OCF ２ CF ２ SO ２ F) CF ２ =CFOCF ２ OCF ２ CF(CF ２ OCF ２ CF ２ SO ２ F)(SO ２ F) The method (P) according to any one of claims 5 to 10, wherein the compound (P) is selected from the group comprising:

12. - steps (a) and (b) are carried out in the presence of a fluorinated solvent, and / or - step (b) is carried out in an inert atmosphere; step (b) is carried out for a time of 2 to 150 hours and / or at a temperature of -60°C to +150°C in the presence of UV radiation, or The method (P) according to any one of claims 5 to 11, wherein step (b) is carried out under heat treatment, preferably by heating at a temperature between 150°C and 250°C.

13. A block copolymer [copolymer (P Ｆ ) ], wherein the first chain end of each of the first and second PFPE chains is a chain end of a copolymer (P), each of which is a perfluorinated linear or branched alkyl chain containing 1 to 6 carbon atoms, —COOH and its organic cation, preferably an onium cation, more preferably ammonium, or an inorganic cation, preferably an alkali metal, more preferably Na ＋ , K. ＋ their salts with, -COOR (wherein R is a linear or branched alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 carbon atom), -COF, -CONH ２ , -CON(R ３００ ) (R ３０１ ) (wherein, R ３００ and R ３０１ each of which has the same meaning as defined for R), -(R) ｃ -OH (wherein c is 0 or 1 and R is as defined above), -C(O)-O-C(O)R (wherein R is as defined above), with the proviso that (i) at least one chain end of the first and second PFPE chains comprises a group other than a perfluorinated linear or branched alkyl chain having 1 to 6 carbon atoms, and (ii) when one chain end comprises the group -COF, the other chain end does not comprise a perfluorinated linear or branched alkyl chain having 1 to 6 carbon atoms or -COF; the second chain ends of the first and second PFPE chains are linked to each other via: at least one first block [block (1)] according to formula (I): -[CR １００ R １０１ -CR １０２ R １０３ ] Ｌ＾ -(D) Ｌ－ (I) (In the formula, L^, L, D, R １００ , R １０１ , R １０２ and R １０３ has the meaning defined above), at least one second block [block (2)] according to formula (II): 【Transformation 7】 (In the formula, m, R ５ ~R ８ has the meaning defined above), and - optionally at least one third block [block (3)] comprising a PFPE chain, However, copolymer (P Ｆ ) inside, the sum of -(L + L^) is 1 to 500, more preferably 2 to 500, more preferably 2 to 300; - the total number of blocks (2) is between 1 and 100; - the at least one block (1), the at least one block (2), and, if present, the at least one block (3), are statistically distributed block copolymers [copolymer (P Ｆ ) ].

14. A block copolymer [copolymer (P Ｏ－Ｏ ) )], wherein each of the first and second PFPE chains is a chain (R ｆ ) or a chain (Rf Ｏ－Ｏ ), where (Rf Ｏ－Ｏ ) is a repeating unit having a peroxide content (PO), defined as grams of active oxygen in 100 g of PFPE peroxy (Mw=16), of between 0.1 and 4, preferably between 0.1 and 3.5, according to any one of formulas (i) to (v) as defined in claim 2 for (R°), wherein each of the first and second PFPE chains has two chain ends, the first chain ends of each of the first and second PFPE chains are chain ends of a copolymer (P) each comprising a group selected from a perfluorinated linear or branched alkyl chain containing 1 to 6 carbon atoms, -C(=O)F and -OC(=O)F, and the second chain ends of the first and second PFPE chains are bonded to each other via: - Formula (I)-[CR １００ R １０１ -CR １０２ R １０３ ]L^-(D) Ｌ - at least one first block [block (1)] according to (I) (In the formula, L^ is an integer from 1 to 250, R １００ , R １０１ , R １０２ and R １０３ are each a halogen atom, more preferably a fluorine or chlorine atom, a linear or branched alkyl chain containing 1 to 6 carbon atoms, -OR ２００ and R ２００ is a linear or branched perfluorinated chain containing 1 to 6 carbon atoms or of the formula -CF ２ OR ２０１ is a group of R ２０１ is a perfluorinated alkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms, or R １００ and R １０１ One of the two and R １０２ and R １０３ is a fluorine atom, and R １００ and R １０１ The other and R １０２ and R １０３ together form a perhalogenated ring having 4 to 6 members, optionally containing a heteroatom such as an oxygen atom, L is 0 or an integer from 1 to 250, D is a group of the formula -(CR １００＊ R １０１＊ -CR １０２＊ R １０３＊ )—, where (D) is —[CR １００ R １０１ -CR １０２ R １０３ ] Ｌ＾ Unlike -, R １００＊ , R １０１＊ , R １０２＊ and R １０３＊ At least one of １００ , R １０１ , R １０２ and R １０３ Unlike provided that if L^ and L are not both 0, the repeat units are statistically distributed. at least one second block [block (2)] according to formula (II) 【Transformation 8】 (In the formula, m is an integer from 1 to 5, R ５ ~R ８ are each independently selected from the group consisting of, or preferably including, -F, a perfluorinated straight or branched alkyl chain having 1 to 6 carbon atoms, and a group of formula (III): (_). ２０ ()) ｙ During the ceremony, R ２０ is a sigma bond or a linear or branched perfluoroalkyl chain containing 1 to 12 carbon atoms and preferably containing and / or interrupted by at least one oxygen atom; X is preferably —SO ２ F, -SO ３ H, —COOH, —COF, —CN, —Br, and —CONH ２ is a functional group selected from y is an integer of 1 or 2; However, in formula (II), R ５ ~R ８ at least one, preferably one, of the formula (III) is a group and - optionally at least one third block [block (3)] comprising a PFPE chain, however, ＊ Copolymer (P Ｏ－Ｏ ) inside, - said block (1), said block (2) and, if present, said at least one block (3) are statistically distributed; the sum of -(L + L^) is at least 1, preferably 1 to 500, more preferably 2 to 500, more preferably 2 to 300; - the total number of blocks (2) is 1 to 100, Ｏ－Ｏ ) ].

15. At least one copolymer (P) according to any one of claims 1 to 4 and at least one of the PFPE peroxys according to claims 5 or 7 and / or a copolymer (P) according to claim 14 Ｏ－Ｏ ). A mixture [Mixture (M1)] comprising one or more of:

16. A block copolymer [copolymer (P Ｆ－Ｏ－Ｏ ) )], wherein each of the first and second PFPE chains is a chain (R ｆ ) or a chain (Rf Ｏ－Ｏ ), where (Rf Ｏ－Ｏ ) is a repeating unit having a peroxide content (PO), defined as grams of active oxygen in 100 g of PFPE peroxy (Mw=16), between 0.1 and 4, preferably between 0.1 and 3.5, according to any one of formulas (i) to (v) as defined in claim 2 for (R°), wherein each of the first and second PFPE chains has two chain ends, the first chain end of each of the first and second PFPE chains being a chain end of a copolymer (P), each of which is a perfluorinated linear or branched alkyl chain containing 1 to 6 carbon atoms, —COOH, and an organic cation, preferably an onium cation, more preferably ammonium, or an inorganic cation, preferably an alkali metal, more preferably Na ＋ , K. ＋ their salts with; -COOR (wherein R is a linear or branched alkyl chain containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 carbon atom); -COF; -CON (R ３００ ) (R ３０１ ) (wherein, R ３００ and R ３０１ each of which is a hydrogen atom or has the same meaning as defined for R; -(R) ｃ -OH (wherein c is 0 or 1 and R is as defined above); -C(O)-O-C(O)R (wherein R is as defined above); -Br; -CN ２ and the second chain ends of the first and second PFPE chains are linked to each other via: at least one first block [block (1)] according to formula (I) -[CR １００ R １０１ -CR １０２ R １０３ ] Ｌ＾ -(D) Ｌ－ (I) (In the formula, L^ is an integer from 1 to 250, R １００ , R １０１ , R １０２ and R １０３ are each a halogen atom, more preferably a fluorine or chlorine atom, a linear or branched alkyl chain containing 1 to 6 carbon atoms, -OR ２００ and R ２００ is a linear or branched perfluorinated chain containing 1 to 6 carbon atoms or of the formula -CF ２ OR ２０１ is a group of R ２０１ is a perfluorinated alkyl chain containing 1 to 6 carbon atoms, optionally interrupted by one or more oxygen ether atoms, or R １００ and R １０１ One of the two and R １０２ and R １０３ is a fluorine atom, and R １００ and R １０１ The other and R １０２ and R １０３ together form a perhalogenated ring having 4 to 6 members, optionally containing a heteroatom such as an oxygen atom, L is 0 or an integer from 1 to 250, D is a group of the formula -(CR １００＊ R １０１＊ -CR １０２＊ R １０３＊ )—, where (D) is —[CR １００ R １０１ -CR １０２ R １０３ ] Ｌ＾ Unlike -, R １００＊ , R １０１＊ , R １０２＊ and R １０３＊ At least one of １００ , R １０１ , R １０２ and R １０３ Unlike provided that if L^ and L are not both 0, the repeat units are statistically distributed. at least one second block [block (2)] according to formula (II) 【Chemistry 9】 (In the formula, m is an integer from 1 to 5, R ５ ~R ８ are each independently selected from the group consisting of, or preferably including, -F, a perfluorinated straight or branched alkyl chain having 1 to 6 carbon atoms, and a group of formula (III): (_). ２０ ()) ｙ During the ceremony, R ２０ is a sigma bond or a linear or branched perfluoroalkyl chain containing 1 to 12 carbon atoms and preferably containing and / or interrupted by at least one oxygen atom; X is preferably —SO ２ F, -SO ３ H, —COOH, —COF, —CN, —Br, and —CONH ２ is a functional group selected from y is an integer of 1 or 2; However, in formula (II), R ５ ~R ８ at least one, preferably one, of the formula (III) is a group and - optionally at least one third block [block (3)] comprising a PFPE chain, however, ＊ Copolymer (P Ｆ－Ｏ－Ｏ ) inside, - said block (1), said block (2) and, if present, said at least one block (3) are statistically distributed; the sum of -(L + L^) is at least 1, preferably 1 to 500, more preferably 2 to 500, more preferably 2 to 300; - the total number of blocks (2) is 1 to 100, Ｆ－Ｏ－Ｏ ) ].

17. At least one copolymer (P) according to claim 13 Ｆ ), and at least one copolymer (P) according to any one of claims 1 to 4, at least one PFPE peroxy according to claim 5 or 7, at least one copolymer (P) according to claim 14 Ｏ－Ｏ ), and / or at least one copolymer (P) according to claim 16 Ｆ－Ｏ－Ｏ ) [Mixture (M2)].

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